Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/08—Macromolecular additives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

Definitions

• the present invention relates to a photocurable resin composition.
• the present invention also relates to an adhesive sheet using the photocurable resin composition, and a method for producing a laminate using the photocurable resin composition.
• Adhesives are used to bond electronic components inside electronic devices such as smartphones and PCs.
• an adhesive sheet is first produced with separators on both sides of the adhesive, and then the adhesive sheet is cut into the desired shape.
• One separator is then peeled off from the cut adhesive sheet, and one side of the exposed adhesive is bonded to a first adherend, and then the other separator is peeled off, and the other side of the exposed adhesive is bonded to a second adherend.
• part of the adhesive sheet is discarded after cutting, resulting in waste.
• Patent Document 1 discloses an invention for providing a radiation-curable adhesive composition that allows fine patterning and exhibits high adhesion to various adherends such as metals, plastics, etc.
• Patent Document 1 describes a radiation-curable adhesive composition that contains 10 to 70% by weight of an ethylenically unsaturated monomer that does not contain an aromatic ring, 1 to 10% by weight of a photopolymerization initiator, and 10 to 55% by weight of a crosslinking agent.
• Patent Document 2 discloses an invention for providing a photocurable adhesive composition that, even when irradiated with light in the presence of oxygen, gives a laminate having adhesive strength equivalent to that in the absence of oxygen.
• Patent Document 2 describes a photocurable adhesive composition that contains (A) a (meth)acrylate oligomer, (B) a monofunctional (meth)acrylic monomer, (C) a di- to tetrafunctional (meth)acrylic monomer, (D) a photoinitiator, (E) a tackifier having a softening point of 70 to 150° C., and (F) a liquid plasticizer.
• the method of printing the adhesive composition into a desired shape and then laminating it to an adherend can suppress the generation of waste.
• a method for curing the adhesive composition a method using light irradiation is preferable to avoid heating the adherend.
• the adhesive composition is not covered with a separator and exposed to oxygen during curing, the outermost surface does not cure and sufficient adhesion may not be obtained. Therefore, in order to prevent oxygen inhibition, it is necessary to seal the adhesive composition with a separator and irradiate it with light in an inert gas atmosphere to cause the reaction to proceed.
• the adhesion is improved by using a material that is not easily inhibited by oxygen, the creep retention may be low, and a photocurable resin composition that is excellent in both adhesion and creep resistance has been desired.
• the present invention aims to provide a photocurable resin composition that has excellent adhesion and creep resistance. It also aims to provide a pressure-sensitive adhesive sheet made using the photocurable resin composition, and a method for producing a laminate made using the photocurable resin composition.
• Disclosure 1 relates to a photocurable resin composition
• a photocurable resin composition comprising a monofunctional (meth)acrylic monomer, a polyfunctional (meth)acrylic monomer, a photopolymerization initiator, and a thermoplastic resin, the thermoplastic resin having a block structure or a graft structure, and having a viscosity at 25°C of 0.001 Pa s or more and 500 Pa s or less.
• Disclosure 2 is the photocurable resin composition of Disclosure 1, wherein the thermoplastic resin contains a thermoplastic resin having a structure derived from styrene.
• the present disclosure 3 relates to the photocurable resin composition of the present disclosure 2, wherein the thermoplastic resin having a structure derived from styrene is a (meth)acrylic/styrene copolymer.
• the present disclosure 4 is the photocurable resin composition of the present disclosure 2 or 3, in which the content ratio of the structure derived from styrene in the thermoplastic resin having the structure derived from styrene is 3 mass% or more.
• the present disclosure 5 is the photocurable resin composition according to the present disclosure 1, 2, 3, or 4, wherein the thermoplastic resin contains a triblock copolymer, and a content ratio of the triblock copolymer in the thermoplastic resin is 50 mass% or more.
• the present disclosure 6 is the photocurable resin composition of the present disclosure 1, 2, 3, 4, or 5, wherein the thermoplastic resin has a weight average molecular weight of 100,000 or more and 500,000 or less.
• the present disclosure 7 is the photocurable resin composition of the present disclosure 1, 2, 3, 4, 5, or 6, wherein the content of the thermoplastic resin in the photocurable resin composition is 1 mass % or more and 60 mass % or less.
• the present disclosure 8 is the photocurable resin composition of the present disclosure 7, wherein the content of the thermoplastic resin in the photocurable resin composition is 10% by mass or more and 40% by mass or less.
• the present disclosure 9 is the photocurable resin composition of the present disclosure 1, 2, 3, 4, 5, 6, 7, or 8, wherein the content of the polyfunctional (meth)acrylic monomer in the photocurable resin composition is 0.3 mass% or more and 40 mass% or less.
• the present disclosure 10 is the photocurable resin composition of the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, or 9, wherein the gel fraction of a cured product obtained by irradiating the photocurable resin composition with ultraviolet light having a wavelength of 395 nm and an illuminance of 500 mW/ cm2 so as to give an irradiation amount of 3000 mJ/cm2 is 25 mass% or more and 60 mass% or less.
• the present disclosure 11 is a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer including a cured product of the photocurable resin composition of the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
• the present disclosure 12 is a pressure-sensitive adhesive sheet according to the present disclosure 11, comprising a substrate and a pressure-sensitive adhesive layer comprising a cured product of the photocurable resin composition on at least one surface of the substrate.
• the present disclosure 13 is a method for producing a laminate, comprising the steps of printing the photocurable resin composition of the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and attaching an adherend using the printed photocurable resin composition.
• the present disclosure 14 is the method for producing a laminate according to the present disclosure 13, wherein the method for printing the photocurable resin composition is screen printing, inkjet printing, or flexographic printing. The present invention will be described in detail below.
• the present inventors investigated the possibility of forming a photocurable resin composition containing a monofunctional (meth)acrylic monomer, a polyfunctional (meth)acrylic monomer, a photopolymerization initiator, and a thermoplastic resin having a block structure or a graft structure, while adjusting the viscosity to a specific range from the viewpoint of printability, etc. As a result, they discovered that it was possible to obtain a photocurable resin composition having excellent adhesion and creep resistance, which led to the completion of the present invention.
• the photocurable resin composition of the present invention contains a monofunctional (meth)acrylic monomer.
• the monofunctional (meth)acrylic monomer is a polymerizable monomer that is polymerized by a reaction of a photopolymerization initiator described later.
• the photocurable resin composition of the present invention has excellent adhesion to various substrates.
• the term "(meth)acrylic” means acrylic or methacrylic
• the term “(meth)acrylic monomer” means a monomer having a (meth)acryloyl group
• the term “(meth)acryloyl” means acryloyl or methacryloyl.
• the term "monofunctional (meth)acrylic monomer” means a monomer having one (meth)acryloyl group in one molecule.
• Examples of the monofunctional (meth)acrylic monomer include monofunctional (meth)acrylic acid ester compounds, monofunctional (meth)acrylamide compounds, and monofunctional (meth)acrylimide compounds.
• Examples of the monofunctional (meth)acrylic acid ester compound include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-heptyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-hydroxybutyl (meth
• acrylate 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, bicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tetrahydrofurfuryl alcohol acrylic acid polymer ester, ethyl carbitol (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, meth)acryl
• Examples of the monofunctional (meth)acrylamide compounds include N,N-dimethyl(meth)acrylamide, N-(meth)acryloylmorpholine, N-hydroxyethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, and N,N-dimethylaminopropyl(meth)acrylamide.
• Examples of the monofunctional (meth)acrylimide compound include N-(meth)acryloyloxyethylhexahydrophthalimide.
• the preferred lower limit of the content of the monofunctional (meth)acrylic monomer in the photocurable resin composition of the present invention is 20% by mass, and the preferred upper limit is 90% by mass.
• the content of the monofunctional (meth)acrylic monomer is within this range, the resulting photocurable resin composition has better adhesion to various substrates.
• the more preferred lower limit of the content of the monofunctional (meth)acrylic monomer is 30% by mass, and the more preferred upper limit is 85% by mass.
• the photocurable resin composition of the present invention contains a polyfunctional (meth)acrylic monomer.
• the polyfunctional (meth)acrylic monomer is a polymerizable monomer that is polymerized by the reaction of a photopolymerization initiator described below, and the polyfunctional (meth)acrylic monomer serves as a crosslinking component.
• the above-mentioned "polyfunctional (meth)acrylic monomer” means a monomer having two or more (meth)acryloyl groups in one molecule.
• polyfunctional (meth)acrylic monomer examples include polyfunctional urethane (meth)acrylates, polyfunctional (meth)acrylic acid ester compounds, and polyfunctional epoxy (meth)acrylates.
• epoxy (meth)acrylate refers to a compound in which all epoxy groups in an epoxy compound have been reacted with (meth)acrylic acid.
• the above-mentioned polyfunctional urethane (meth)acrylate can be obtained, for example, by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound in the presence of a catalytic amount of a tin-based compound.
• MDI diphenylmethane-4,4'-
• isocyanate compound serving as a raw material for the polyfunctional urethane (meth)acrylate a chain-extended isocyanate compound obtained by reacting a polyol with an excess of an isocyanate compound can also be used.
• the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.
• Examples of the (meth)acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono(meth)acrylates, mono(meth)acrylates of dihydric alcohols, and mono(meth)acrylates or di(meth)acrylates of trihydric alcohols.
• Examples of the hydroxyalkyl mono(meth)acrylate include 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, and 4-hydroxybutyl(meth)acrylate.
• Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol.
• Examples of the trihydric alcohol include trimethylolethane, trimethylolpropane, and glycerin.
• polyfunctional (meth)acrylic acid ester compounds examples include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide-added
• polyfunctional epoxy (meth)acrylate examples include bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, bisphenol E type epoxy (meth)acrylate, and caprolactone modified versions of these.
• the preferred lower limit of the content of the polyfunctional (meth)acrylic monomer in the photocurable resin composition of the present invention is 0.3% by mass, and the preferred upper limit is 40% by mass.
• the content of the polyfunctional (meth)acrylic monomer is within this range, the resulting photocurable resin composition has better adhesion to various substrates and creep resistance.
• the more preferred lower limit of the content of the polyfunctional (meth)acrylic monomer is 0.5% by mass, and the more preferred upper limit is 30% by mass.
• the photocurable resin composition of the present invention preferably contains a compound having a cyclic structure containing a nitrogen atom (hereinafter also referred to as a "nitrogen-containing ring compound”) as a polymerizable monomer.
• a nitrogen-containing ring compound a compound having a cyclic structure containing a nitrogen atom
• the nitrogen-containing ring compound may be one contained in the monofunctional (meth)acrylic monomer or the polyfunctional (meth)acrylic monomer, or may not be one contained in the monofunctional (meth)acrylic monomer or the polyfunctional (meth)acrylic monomer.
• the nitrogen-containing cyclic compound preferably contains at least one selected from the group consisting of monofunctional radically polymerizable monomers having a lactam structure and maleimide derivatives, and more preferably contains a maleimide derivative.
• the reaction system of the monofunctional radical polymerizable monomer having the lactam structure and the maleimide derivative basically proceeds by a hydrogen abstraction (Type II) reaction. Photoradical polymerization by hydrogen abstraction reaction is not easily inhibited by oxygen, and can increase the surface curability. In addition, photoradical polymerization by hydrogen abstraction reaction does not produce a linear polymer like cleavage (Type I) reaction, but a branched polymer, and the cohesive force is also high.
• the photocurable resin composition obtained can obtain a cured product that is less likely to cause bleeding due to a decrease in surface curability and cohesive failure due to a decrease in surface curability and cohesive force.
• examples of the monofunctional maleimide include N-cyclohexylmaleimide, N-laurylmaleimide, 4-hydroxyphenylmaleimide, N-(4-carboxycyclohexylmethyl)maleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(2-chlorophenyl)maleimide, N-methylmaleimide, and N-ethylmaleimide.
• maleimide examples include N-isopropylmaleimide, N-butylmaleimide, N-benzylmaleimide, N-phenylmethylmaleimide, N-(2,4,6-tribromophenyl)maleimide, N-(3-(triethoxysilyl)propyl)maleimide, N-octadecenylmaleimide, N-dodecenylmaleimide, N-(2-methoxyphenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, and N-(1-hydroxyphenyl)maleimide.
• the monofunctional maleimide is preferably at least one selected from the group consisting of N-cyclohexylmaleimide, 4-hydroxyphenylmaleimide, and N-(4-carboxycyclohexylmethyl)maleimide, and more preferably N-cyclohexylmaleimide.
• examples of polyfunctional maleimides include N,N'-methylene bismaleimide, N,N'-trimethylene bismaleimide, N,N'-dodecamethylene bismaleimide, N,N'-(4,4'-diphenylmethane) bismaleimide, 1,4-dimaleimidecyclohexane, isophorone bisurethane bis(N-ethylmaleimide), N,N'-P-phenylene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-m-toluylene bismaleimide, and N,N'-4,4'-biphenyl.
• maleimide derivatives examples include N,N'-4,4'-(3,3'-dimethyl-biphenylene)bismaleimide, N,N'-4,4'-(3,3'-dimethyldiphenylmethane)bismaleimide, N,N'-4,4'-(3,3'-diethyldiphenylmethane)bismaleimide, N,N'-4,4'-diphenylpropane bismaleimide, N,N'-4,4'-diphenylether bismaleimide, N,N'-3,3'-diphenylsulfone bismaleimide, and N,N'-4,4'-diphenylsulfone bismaleimide. From the viewpoint of increasing the reaction rate, the above monofunctional maleimide may be used in combination with these polyfunctional maleimides as the maleimide derivatives, but it is not preferable to use a large amount of polyfunctional maleimide in combination since the gel fraction increases.
• the monofunctional radically polymerizable monomer having a lactam structure is preferably a compound represented by the following formula (1):
• n represents an integer from 2 to 6.
• Examples of the compound represented by the above formula (1) include N-vinyl-2-pyrrolidone and N-vinyl- ⁇ -caprolactam. Among these, N-vinyl- ⁇ -caprolactam is preferred.
• the preferred lower limit of the content of the nitrogen-containing ring compound in the photocurable resin composition of the present invention is 0.1% by mass, and the preferred upper limit is 30% by mass.
• the content of the nitrogen-containing ring compound is within this range, the resulting pressure-sensitive adhesive sheet has superior surface curing properties and adhesion to various substrates.
• a more preferred lower limit of the content of the nitrogen-containing ring compound is 0.5% by mass, and a more preferred upper limit is 25% by mass.
• the photocurable resin composition of the present invention contains a photopolymerization initiator.
• the photopolymerization initiator preferably includes at least one selected from the group consisting of hydrogen abstraction type photopolymerization initiators and polymer type photopolymerization initiators.
• the obtained cured product is less likely to suffer from bleeding due to a decrease in surface curability, or cohesive failure due to a decrease in surface curability and cohesive force.
• the photopolymerization initiator more preferably includes a polymer type photopolymerization initiator.
• polymeric photopolymerization initiator examples include polymers of ethyl (2,4,6-trimethylbenzoyl)-phenyl phosphonate, polyethylene glycol di( ⁇ -4(4-(2-dimethylamino-2-benzyl)butanoylphenyl)piperazine)propionate, and bis(benzophenone-2-carboxylic acid) polyethylene glycol ester.
• Omnipol TP Omnipol 910
• Omnipol 2702 All manufactured by IGM Resins.
• a benzophenone-based photopolymerization initiator is preferable.
• the benzophenone-based photopolymerization initiator include benzophenone, 4-chlorobenzophenone, 4,4'-dimethylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, o-benzoyl methyl benzoate, 3,3'-dimethyl-4-methoxybenzophenone, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 4-morpholinobenzophenone, 4,4'-diphenoxybenzophenone, 4-hydroxybenzophenone, 2-carboxybenzophenone, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methyl-propionyl)-benzyl)-phenyl)-2-methyl-propan-1-one, 1-(4-(4-benzoylphenylthio)phenyl)-2-to
• cleavage type photopolymerization initiator As the photopolymerization initiator, a cleavage type photopolymerization initiator can also be used.
• the cleavage type photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.
• the preferred lower limit of the content of the photopolymerization initiator in the photocurable resin composition of the present invention is 1 mass%, and the preferred upper limit is 15 mass%.
• the resulting photocurable resin composition has better storage stability and curability, and the resulting pressure-sensitive adhesive sheet has better adhesion to various substrates.
• a more preferred lower limit of the content of the photopolymerization initiator is 3 mass%, and a more preferred upper limit is 8 mass%.
• the photocurable resin composition of the present invention contains a thermoplastic resin.
• the thermoplastic resin has a block structure or a graft structure.
• the photocurable resin composition of the present invention has excellent creep resistance.
• the thermoplastic resin preferably has a block structure.
• the block structure or the graft structure may be present in any part of the molecule of the thermoplastic resin, and a random structure may be present in the other part.
• Even if the thermoplastic resin is a polymer of two or more monomers having a common structure, if the two or more monomers are different compounds and have a block structure or a graft structure, it is treated as a thermoplastic resin having a block structure or a graft structure.
• An example of such a polymer is an acrylic triblock copolymer derived from three types of acrylic monomers.
• the thermoplastic resin preferably contains a thermoplastic resin having a structure derived from styrene or a thermoplastic resin having a structure derived from a (meth)acrylic compound.
• a thermoplastic resin having a structure derived from styrene or a thermoplastic resin having a structure derived from a (meth)acrylic compound By containing the thermoplastic resin having a structure derived from styrene or a thermoplastic resin having a structure derived from a (meth)acrylic compound, the resulting photocurable resin composition has better creep resistance.
• the thermoplastic resin contains a thermoplastic resin having a structure derived from styrene.
• thermoplastic resins having a structure derived from styrene include (meth)acrylic/styrene copolymers, butadiene/styrene, isoprene/styrene, ethylenebutylene/styrene, ethylenepropylene/styrene, etc.
• (meth)acrylic/styrene copolymers are preferred from the viewpoints of compatibility with monofunctional (meth)acrylic monomers and polyfunctional (meth)acrylic monomers and improved creep resistance.
• the preferred lower limit of the content of the styrene-derived structure in the thermoplastic resin having the styrene-derived structure is 3% by mass.
• the content of the styrene-derived structure is 3% by mass or more, the resulting photocurable resin composition has better creep resistance.
• the more preferred lower limit of the content of the styrene-derived structure is 4% by mass.
• the upper limit of the content of the styrene-derived structure in the thermoplastic resin having a styrene-derived structure is preferably 40 mass%, more preferably 30 mass%.
• thermoplastic resins having a structure derived from the above (meth)acrylic compound include poly(meth)acrylate, acrylonitrile/styrene/(meth)acrylic copolymer, (meth)acrylic/styrene copolymer, ethylene/(meth)acrylic copolymer/acrylic/methacrylic copolymer, etc.
• (meth)acrylic/styrene copolymer is preferred from the viewpoint of compatibility with monofunctional (meth)acrylic monomers and polyfunctional (meth)acrylic monomers and improved creep resistance.
• the thermoplastic resin preferably contains a triblock copolymer.
• the thermoplastic resin which is a triblock copolymer By containing the thermoplastic resin which is a triblock copolymer, the resulting photocurable resin composition has better creep resistance.
• the thermoplastic resin contains a (meth)acrylic/styrene-based triblock copolymer as the ABA type triblock copolymer.
• the thermoplastic resin has a weight average molecular weight of preferably 100,000 at the lower limit and 500,000 at the upper limit. When the weight average molecular weight of the thermoplastic resin is within this range, the resulting photocurable resin composition has better creep resistance.
• the weight average molecular weight of the thermoplastic resin is more preferably 150,000 at the lower limit and 400,000 at the upper limit.
• the weight average molecular weight can be determined, for example, by measuring the molecular weight distribution in terms of polystyrene using gel permeation chromatography (GPC). Specifically, for example, the weight average molecular weight can be determined by measuring under the following conditions using gel permeation chromatography (Waters Corporation, "2690 Separations Module” or the like).
• Solvent Tetrahydrofuran Sample flow rate: 1 mL/min Detector: Differential refractometer RI Column: GPC KF-806L (Showa Denko) Column temperature (measurement temperature): 40°C Injection volume: 20 ⁇ L
• the preferred lower limit of the content of the thermoplastic resin in the photocurable resin composition of the present invention is 1 mass%, and the preferred upper limit is 60 mass%. When the content of the thermoplastic resin is within this range, the resulting photocurable resin composition has better creep resistance.
• the more preferred lower limit of the content of the thermoplastic resin is 10 mass%, and the more preferred upper limit is 40 mass%.
• the photocurable resin composition of the present invention preferably further contains a tackifier.
• a tackifier include rosin-based resins and terpene-based resins.
• the rosin-based resin includes, for example, rosin diol.
• the rosin diol is not particularly limited as long as it is a rosin-modified diol having two rosin skeletons and two hydroxyl groups in the molecule.
• Diols having a rosin component in the molecule are called rosin polyols, and these include polyether types such as polypropylene glycol (PPG) in which the skeleton excluding the rosin component is polyether, and polyester types such as condensation polyester polyols, lactone polyester polyols, and polycarbonate diols.
• PPG polypropylene glycol
• polyester types such as condensation polyester polyols, lactone polyester polyols, and polycarbonate diols.
• rosin diol examples include rosin ester obtained by reacting rosin with a polyhydric alcohol, epoxy-modified rosin ester obtained by reacting rosin with an epoxy compound, and modified rosin having a hydroxyl group, such as polyether having a rosin skeleton, etc. These can be produced by conventionally known methods.
• rosin components include, for example, abietic acid, abietic acid derivatives such as dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, diabietic acid, and neoabietic acid, pimaric acid-type resin acids such as levopimaric acid, hydrogenated rosins obtained by hydrogenating these, and disproportionated rosins obtained by disproportionating these.
• rosin-based resins include Pine Crystal D-6011, Pine Crystal KE-615-3, Pine Crystal KR-614, Pine Crystal KE-100, Pine Crystal KE-311, Pine Crystal KE-359, Pine Crystal KE-604, and Pine Crystal D-6250 (all manufactured by Arakawa Chemical Industries Co., Ltd.).
• the terpene resin examples include terpene phenol resins.
• the terpene phenol resin is a copolymer of phenol and a terpene resin, which is an essential oil component obtained from natural products such as rosin and orange peel, and also includes partially hydrogenated terpene phenol resins in which at least a portion of the copolymer is hydrogenated, and fully hydrogenated terpene phenol resins in which the copolymer is completely hydrogenated.
• the fully hydrogenated terpene phenolic resin is a terpene resin obtained by substantially completely hydrogenating a terpene phenolic resin
• the partially hydrogenated terpene phenolic resin is a terpene resin obtained by partially hydrogenating a terpene phenolic resin.
• the terpene phenolic resin has a double bond derived from a terpene and an aromatic ring double bond derived from a phenol. Therefore, the fully hydrogenated terpene phenolic resin means a resin in which both the terpene portion and the phenol portion are completely or almost hydrogenated, and the partially hydrogenated terpene phenolic resin means a resin in which the degree of hydrogenation of these portions is not complete but partial.
• the hydrogenation method and reaction form are not particularly limited.
• examples of commercially available ones include YS Polystar NH (fully hydrogenated terpene phenol-based resin) manufactured by Yasuhara Chemical Co., Ltd.
• the preferred lower limit of the content of the tackifier in the photocurable resin composition of the present invention is 5% by mass, and the preferred upper limit is 50% by mass. When the content of the tackifier is within this range, the resulting photocurable resin composition has better adhesion to various substrates.
• the more preferred lower limit of the content of the tackifier is 10% by mass, and the more preferred upper limit is 40% by mass.
• the photocurable resin composition of the present invention may contain a filler from the viewpoint of improving printability by adjusting the viscosity.
• a filler from the viewpoint of improving printability by adjusting the viscosity.
• an inorganic filler or an organic filler can be used.
• the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, and calcium silicate.
• the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and (meth)acrylic polymer fine particles. Of these, silica is preferred, and fumed silica is more preferred.
• the preferred lower limit of the filler content in the photocurable resin composition of the present invention is 0.3% by mass, and the preferred upper limit is 15% by mass. By having the filler content within this range, the obtained photocurable resin composition can easily adjust the viscosity while maintaining excellent adhesion.
• the more preferred lower limit of the filler content is 0.5% by mass, and the more preferred upper limit is 10% by mass.
• the photocurable resin composition of the present invention may contain an antifoaming agent from the viewpoint of improving printability, etc.
• the defoaming agent include silicone-based defoaming agents, acrylic polymer-based defoaming agents, vinyl ether polymer-based defoaming agents, and olefin polymer-based defoaming agents.
• the preferred lower limit of the content of the defoaming agent in the photocurable resin composition of the present invention is 0.3% by mass, and the preferred upper limit is 5% by mass. When the content of the defoaming agent is within this range, the resulting photocurable resin composition has better printability.
• the more preferred lower limit of the content of the defoaming agent is 0.5% by mass, and the more preferred upper limit is 3% by mass.
• the photocurable resin composition of the present invention may further contain various known additives such as a plasticizer, a silane coupling agent, a sensitizer, a heat curing agent, a curing retarder, an antioxidant, a storage stabilizer, and a dispersant, as long as the object of the present invention is not impaired.
• a plasticizer such as a polystyrene, polystyrene, polystyrene, polysulfate, polysulfate, polysulfate, polysulfate, polysulfate, polymethyl methacrylate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate,
• the photocurable resin composition of the present invention can be prepared, for example, by using a mixer to mix the monofunctional (meth)acrylic monomer, the polyfunctional (meth)acrylic monomer, the photopolymerization initiator, the thermoplastic resin, and additives to be added as necessary.
• a mixer examples include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mixer.
• the photocurable resin composition of the present invention is suitable for printing. If an adhesive layer is formed by applying the desired pattern onto an adherend (substrate) by printing, there is an advantage that the cutting process can be omitted compared to the case where an adhesive sheet is cut just before lamination to obtain an adhesive of the desired shape. As a result, it is possible to suppress the generation of waste and reduce the environmental burden.
• the lower limit of the viscosity of the photocurable resin composition of the present invention at 25° C. is 0.001 Pa ⁇ s, and the upper limit is 500 Pa ⁇ s. When the viscosity is within this range, the photocurable resin composition of the present invention is suitable for printing.
• the lower limit of the viscosity is preferably 0.01 Pa ⁇ s, and the upper limit is preferably 300 Pa ⁇ s, and more preferably 0.1 Pa ⁇ s, and the upper limit is more preferably 100 Pa ⁇ s.
• the viscosity can be measured, for example, by using a VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) as an E-type viscometer and selecting an appropriate rotation speed from 1 to 100 rpm based on the optimal torque number in each viscosity range with a CP1 cone plate.
• VISCOMETER TV-22 manufactured by Toki Sangyo Co., Ltd.
• the photocurable resin composition of the present invention is irradiated with ultraviolet light having a wavelength of 395 nm and an illuminance of 500 mW/cm2 so that the exposure dose is 3000 mJ/ cm2 .
• the gel fraction of the cured product obtained by irradiating the photocurable resin composition with ultraviolet light having a wavelength of 395 nm and an illuminance of 500 mW/ cm2 is preferably 25% by mass or more and 60% by mass or more. When the gel fraction of the cured product is in this range, the resulting photocurable resin composition has better adhesion and creep resistance after curing.
• the lower limit of the gel fraction of the cured product is more preferably 30 mass %, and the upper limit is more preferably 50 mass %.
• the gel fraction of the cured product can be measured by the following method. That is, first, the photocurable resin composition is irradiated with ultraviolet light having a wavelength of 395 nm and an illuminance of 500 mW/cm 2 so that the irradiation amount is 3000 mJ/cm 2 to obtain a cured product. 0.15 g of the obtained cured product is weighed into a glass bottle, and then immersed in 30 g of tetrahydrofuran and immersed with shaking at 23 ° C. for 24 hours. Next, the cured product is taken out through a 200 mesh filter, and then heated and dried at 110 ° C. for 1 hour.
• the mass of the cured product is then measured, and the gel fraction can be calculated by the following formula.
• Gel fraction (mass%) ( W2 / W1 ) ⁇ 100
• W1 Mass of the cured product before immersion in tetrahydrofuran at 23°C.
• W2 Mass of the cured product after immersion in tetrahydrofuran at 23°C, removal, and drying
• the photocurable resin composition of the present invention is coated on a substrate and irradiated with ultraviolet light having a wavelength of 395 nm and an illuminance of 500 mW/ cm2 at an irradiation dose of 3000 mJ/ cm2 , and the cured product has a glass transition temperature of preferably -10°C at its lower limit and 25°C at its upper limit.
• the glass transition temperature of the cured product is within this range, the photocurable resin composition obtained has better adhesion to various substrates.
• the more preferred lower limit of the glass transition temperature of the cured product is -5°C, and the more preferred upper limit is 15°C.
• the glass transition temperature of the cured product can be measured by the following method.
• the photocurable resin composition is coated on a release PET film as a substrate, and then, using an ultraviolet irradiation device, ultraviolet rays having a wavelength of 395 nm and an illuminance of 500 mW/ cm2 are irradiated to an irradiation amount of 3000 mJ/ cm2 to cure the photocurable resin composition and obtain a cured product.
• the glass transition temperature of the resulting cured product can be determined as the tan ⁇ peak temperature when dynamic viscoelasticity measurement is performed under the following conditions using a dynamic viscoelasticity measuring device.
• the dynamic viscoelasticity measuring device for example, DVA-200 (manufactured by IT Measurement & Control Co., Ltd.) can be used.
• the photocurable resin composition of the present invention can form an adhesive layer by curing it with ultraviolet light, and the method of use may be to form an adhesive layer on a substrate (separator) to produce an adhesive sheet that can be transferred to an adherend, or to form an adhesive layer directly on an adherend.
• the method of forming an adhesive layer directly on an adherend the number of times of lamination can be minimized and air bubbles can be prevented from entering the interface during lamination.
• the adhesive layer is placed on the adherend by transfer, which has the advantage of fewer constraints on construction.
• the present invention also includes a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing a cured product of the photocurable resin composition of the present invention.
• the pressure-sensitive adhesive sheet of the present invention may be a non-support type pressure-sensitive adhesive sheet that does not have a substrate, or it may be a supported type pressure-sensitive adhesive sheet, i.e., a pressure-sensitive adhesive sheet having a substrate and a pressure-sensitive adhesive layer containing a cured product of the photocurable resin composition of the present invention on at least one surface of the substrate.
• the pressure-sensitive adhesive sheet of the present invention may be a single-sided pressure-sensitive adhesive sheet having the above-mentioned pressure-sensitive adhesive layer on one side of the substrate, or a double-sided pressure-sensitive adhesive sheet having the above-mentioned pressure-sensitive adhesive layer on both sides.
• the substrate examples include sheets made of resins such as acrylic, olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), nylon, urethane, and polyimide, sheets with a mesh structure, and sheets with holes.
• resins such as acrylic, olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), nylon, urethane, and polyimide
• the present invention also includes a method for producing a laminate, which includes a step of printing the photocurable resin composition of the present invention and a step of attaching an adherend using the printed photocurable resin composition.
• examples of the method for printing the photocurable resin composition of the present invention include screen printing, inkjet printing, flexographic printing, gravure printing, slot die coating, knife coating, spray coating, spin coating, stencil printing, dispensing, jet dispensing, and reverse offset printing.
• screen printing, inkjet printing, and flexographic printing are preferred, and screen printing is more preferred.
• Examples of the material of the adherend include metals such as stainless steel and aluminum, and resins.
• the present invention it is possible to provide a photocurable resin composition having excellent adhesion and creep resistance.
• the weight average molecular weight of the obtained acrylic graft polymer A was measured by gel permeation chromatography (Waters Corporation, "2690 Separations Module” or the like) under the following conditions. ⁇ Conditions> Solvent: Tetrahydrofuran Sample flow rate: 1 mL/min Detector: Differential refractometer RI Column: GPC KF-806L (Showa Denko) Column temperature (measurement temperature): 40°C Injection volume: 20 ⁇ L
• Each of the obtained photocurable resin compositions was applied to the inner treated surface of an easily adhesive polyester film (manufactured by Toyobo Co., Ltd., "Cosmoshine A4100") with an applicator. Thereafter, without sealing the coated surface, the film was irradiated with ultraviolet light having a wavelength of 395 nm and an illuminance of 500 mW/cm2 in an atmospheric environment using a batch-type UV LED curing device (manufactured by CSS, "UV-LED PROCESSOR LSS-61”) so that the irradiation amount was 3000 mJ/ cm2 , thereby obtaining a cured product having a thickness of 50 ⁇ m.
• an easily adhesive polyester film manufactured by Toyobo Co., Ltd., "Cosmoshine A4100
• the film was irradiated with ultraviolet light having a wavelength of 395 nm and an illuminance of 500 mW/cm2 in an atmospheric environment using a batch-
• the illuminance and the integrated light amount were measured using a UV irradiation meter UVR-T2 and a light receiving unit UD-T36T2 (manufactured by TOPCON Corporation).
• the air surface was sealed with a release PET film (manufactured by Nippa, "1-C", thickness 38 ⁇ m), and cut to a width of 25 mm and a length of 200 mm (adhering surface 25 mm ⁇ 125 mm) to prepare a laminated film.
• the release PET film was peeled off from the laminated film, and the exposed surface was attached to a SUS substrate and pressed by moving it back and forth with a 2 kg roller to obtain a test piece.
• test piece was stored in an environment of 25 ° C. for 24 hours, and a universal testing machine (manufactured by A & D, "Tensilon RTI-1310") was used to perform a 180 ° peel at a speed of 300 mm / min to measure the 180 ° peel adhesive strength.
• a universal testing machine manufactured by A & D, "Tensilon RTI-1310"
• the other release PET film (1-E) was peeled off, and the mirror-polished surface of a similar SUS substrate was attached to the exposed cured product surface, and then the specimen was pressed at 215 N using a universal testing machine (manufactured by A&D Co., Ltd., "Tensilon RTI-1310") and allowed to stand for 24 hours in an environment of 25°C to obtain a test specimen.
• the obtained test piece was hung from one of the SUS substrates by an S-hook, and furthermore, a weight of 1 kg was hung from the other SUS substrate. This was left at 25° C., and the time until the weight fell was measured, and the creep resistance was evaluated according to the following criteria.
• ⁇ The weight did not fall even after 48 hours had passed.
• ⁇ The time until the weight fell was 24 hours or more but less than 48 hours.
• ⁇ The time until the weight fell was less than 24 hours.
• a pattern-treated 80-mesh printing plate was used as the screen printing plate.
• a batch-type UV LED curing device (CSS Corporation, "UV-LED PROCESSOR LSS-61") was used to irradiate the film with ultraviolet light having a wavelength of 395 nm and an illuminance of 500 mW/cm 2 so that the irradiation amount was 3000 mJ/cm 2 , thereby obtaining a cured product having a thickness of 50 ⁇ m.
• the present invention it is possible to provide a photocurable resin composition having excellent adhesion and creep resistance.

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